Dimerization of c3 to c18 olefins



Nov. l2, 1968 H. H. EBY ET AL DIMERIZATION OF C3 TO Cl@ OLEFINS med May 14. 1964 2 Sheets-Sheet 1 E: ESOS uhmm OP MMVI ||- H, EBY ET ALv 3,410,925

DIMERIZATION OF C3 TO 0,6 OLEFINS 2 Sheets-Sheet 2 Nov. l2, 1968 Filed may 14, 1964 United States Patent O 3,410,925 DIMERIZATION OF C3 TO C18 OLEFINS Harold H. Eby and Gerald L. Nield, Ponca City, Okla.,

Kyle W. Resh, Baltimore, Md., and John H. Smith,

Ponca City, Okla., assignors to Continental Oil Company, Ponca City, Okla., a corporation of Delaware Filed May 14, 1964, Ser. No. 367,417 5 Claims. (Cl. 260-683.15)

The present invention relates to alkyl aromatic hydrocarbons and, more particularly, to alkyl aromatic hydrocarbons which are suitable for preparing oil-soluble sulfonates. In one aspect, the invention relates to processes for preparing alkyl aromatic hydrocarbons. In another aspect the invention relates to alkyl aromatic hydro carbons which are particularly suitable for preparing oilsoluble sulfonates as a composition of matter.

Many uses exist for oil-soluble sulfonates in modern technology. One use, which has accounted for the consumption of large quantities of oil-soluble sulfonates, is as an additive in lubricants. Sulfonates are used in lubricants either per se or as the so-called superbased detergents.

One of the earliest methods of producing oil-soluble sulfonates was that of treating aromatic-containing petroleum fractions with sulfuric acid. The sulfonates so produced were known to the trade as mahogany sulfonates. In general, these sulfonates were a by-product of the manufacture of lubricating oil base 4stocks or white oils. inasmuch as they were a by-product, the supply of the materials was related to the amount of lubricating oil base stocks which were acid treated. The development of improved methods of preparing lubricating oil base `stocks has substantially reduced the supply of mahogany sulfonates. 1

More recently, a particularly satisfactory source of alkyl aromatic hydrocarbons suitable for preparing oilsoluble sulfonates has been a by-product of the preparation of dodecylbenzene. As is well known, dodecylbenzene is prepared by the alkylation of benzene with propylene tetramer using a Friedel-Crafts catalyst. In addition to the primary product (i.e., dodecylbenzene) a number of other alkyl aromatic hydrocarbon fractions are produced. The bottoms fraction resulting from the distillation of the alkylation reaction product is known in the industry as postdodecylbenzene or polydodecylbenzene. While this postdodecylbenzene is quite satisfactory as a feedstock for preparing oil-soluble sulfonates, it has the disadvantage that the availability thereof is directly tied to the production of the primary product, dodecylbenzene.

It lis an object of the present invention to provide as a composition of matter alkyl aromatic hydrocarbons which are particularly suitable for preparing oil-soluble sulfonates.

lt is another object of the invention to provide processes for preparing alkyl aromatic hydrocarbons which are particularly useful for preparing oil-soluble sulfonates.

It is a particular object of the invention to provide a process for preparing alkyl aromatic hydrocarbons wherein the sludge from the alkylation reaction is used as a catalyst in a polymerization step.

Broadly stated, the invention relates to alkyl aromatic hydorcarbons which are particularly suitable for preparing oil-soluble sulfonates and, broadly stated, have the following properties: mono, branched, long-chain alkyl aryl content of greater than 50' percent, a molecular weight greater than 320, and a boiling range above 325 F. at 20' mm. Hg pressure.

The invention relates also to the perparation of alkyl aromatic hydrocarbons, which are particularly suitable for preparing oil-soluble sulfonates, by a process comprising, in general, the following steps:

(a) Dimerization of a suitable feedstock.

lCe

(b) Alkylation of an aromatic hydrocarbon with the dimer formed in step (a).

Preferably, the aromatic hydrocarbon is either benzene or toluene.

In a preferred aspect the invention relates to the preparation of alkyl aromatic hydrocarbons comprising, in general, the following steps:

(a) Dimerization of a suitable feedstock using a Friedel-Crafts alkylation sludge as the catalyst therefor.

(b) Alkylation of an aromatic hydrocarbon with the dimer of step (a) in the presence of a Friedel-Crafts catalyst.

Preferably, the aromatic hydrocarbon is ether benzene or toluene, and the process produces an alkyl aromatic hydrocarbon which is useful for preparing an oil-soluble sulfonate. t

It may be well to state at this time that the terms dimer and dimerization are used herein for reason of convenience and not by way of limitation. It is believed that polymerization reactions other than dimerization occur in the first step of our process. For example, some C5 olens may be trimerized to C15 and some C1, materials may be polymer-ized to a C16 or C211. A substantial amount of the olefins is dimerized. For this reason, we have chosen to use the terms dimer and dimerization Having stated the nature `of our invention, it is now convenient to discuss briefly the advantages thereof as compared to the prior art. Our invention possesses two salient features. First, the process is one wherein the primary product is an alkyl aromatic hydrocarbon which is suitable for preparing an oil-soluble sulfonate. This is in direct contrast to the process for preparing dodecylbenzene, wherein postdodecylbenzene is a by-product. Secondly, the alkyl aromatic hydrocarbon of our invention, as produced by the process of our invention, is an improved sulfonation feedstock. Presumably, this is due to the high mono alkyl content of our product. This feature will be discussed in more detail further on in this application.

As indicated previously, either of two processes can be used to prepare the alkyl aromatic hydrocarbon of our invention. Both processes involve two general steps, dimerization and alkylation. These processes will now be discussed in greater detail.

According to the iirst process, a suitable olefnic feedstock is dimerized in the presence of mineral acid catalyst. Following this reaction, the spent acid :is separated from the reaction mass which is then washed with a caustic solution; followed by separation of the desired olefin dimer. The desired olefin dimer is then used to alkylate an aromatic hydrocarbon using a Friedel`Crafts catalyst. The alkylation reaction product is subjected to an acidic Wash, after which the spent acid sludge is removed. The material is then washed again with a caustic solution. The washed reaction product is then subjected to a distillation to recover the dimer alkylate bottoms which is the desired material.

Suitable feedstocks for our process include a Wide variety of oleiinic hydrocarbons and mixtures of olenic hydrocarbons. In general, these olenc hydrocarbons contain from 3 to 18 carbon atoms. Examples of suitable olelinic hydrocarbons include propene, butene, pentene, hexene, heptene, octene, nonene, decene, hendecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, and octadecene.` These suitable olefin hydrocarbons can be either straight or branchedchain. In addition, the feedstock can contain olefins containing rnore than 18 carbon atoms. However, these materials will pass through the reaction without undergoing dimerization.

The more suitable oletinic hydrocarbons for feedstocks include those containing from 5 to 12 carbon atoms, in other words, from the pentenes to the dodecenes. These also can be either straight or branched chain.

A preferred olefinic hydrocarbon is the material known to the petroleum industry as cat poly gasoline which is a mixture of predominantly branched chain olefins containing, generally, from about 5 to about 12 carbon atoms. Thisl material is produced by the polymerization of propylene. It is prepared by passage of propylene through a catalytic polymerization unit. For additional information, we refer to the following reference, which is made a part of this disclosure: Hydrocarbon Processing and Petroleum Refiner, 41, 190 (September 1962). A representative sample of cat poly gasoline has the following composition, as determined by GLPC 1 analysis:

No. of carbon atoms- Percent `C5 5 C6 3 C7 7 C8 16 C9 35 C10 17 C11 11 C12 5 Cat poly gasolines having the following distillation range can be used in our process.

Suitable, F. Preferred, F.

1.13.1. Range 86-500 135-360 50% Range 10G-500 280-385 End Point Range 125-750 425-525 Another preferred olefinic hydrocarbon for use as a feedstock is the dodecene fraction obtained from a catalytic polymerization unit. This material is obtained by recycling through the unit until a product comprising a mixture of olefins having a peak at C12 is obtained. A representative dodecene has the following properties:

Of the preceding olefinic hydrocarbons, cat poly gasoline is more preferred because of availability and cost.

In this aspect of our invention the dimerization is conducted using a mineral acid catalyst, with sulfuric acid being preferred. A suitable sulfuric acid is from 80 to 108 percent, with a preferred sulfuric acid being from 95 to 100 percent. A suitable quantity of acid is from about 0.02 to about 0.7 part (weight) per part of the olefin, with a preferred quantity being from about 0.15 to about 0.30 part (weight).

In general, presssure, temperature, and residence time are not critical in the dimerization step. Atmospheric (or ambient) pressure is preferred for reasons of economy, although it is feasible to operate at either slightly elevated or reduced pressures. We have found that the process 1GLPC refers to gas liquid partition chromatography or vapor phase chromatography, an accepted analytical toch` nlque.

operates satisfactorily at temperatures in the range of about 10 to about 75 C., with temperatures of about 20 to about 55 C. being preferred. Any residence time greater than 5 minutes is satisfactory for the process.

Distillation range for typical dimers prepared using a mineral acid catalyst are shown in the examples.

As indicated previously, the second step of the first aspect is the alkylation of an aromatic hydrocarbon with the dimer.

Inasmuch as this alkylation step. is the same in both aspects of our process, it will be described later in connection with the second aspect.

In the second and preferred aspect of our process the olefin dimerization is conducted using the sludge from the alkylation reaction as a catalyst. This aspect has several advantages. As one advantage, the catalyst is the same for both dimerization and alkylation steps. As another advantage, no dimer clean up is required prior to the alkylation step. We have found it feasible to transfer the entire reaction mass from the dimerization step to the alkylation reaction zone. The olefinic hydrocarbons which can be used as a feedstock are the same as those described in connection with. the first aspect.

The catalyst used in this aspect is the sludge derived from the alkylation of the aromatic hydrocarbon with the olefin dimer using a Friedel-Crafts catalyst. The Friedel-Crafts catalysts will be described in more detail in our description of the -alkylation reaction.

A satisfactory start up sludge for use in the dimerization step can -be produced by the alkylation of an aromatic hydrocarbon (e.g., benzene) with cat poly gasoline (or other suitable olefins). After the process is on stream the required amount of the alkylation sludge is recycled to the dimerization step.

We have found that a suitable quantity of sludge for the dimerization step is in the range of about 0.25 'part to about 4.0 parts (weight) per part of olefinic hydrocarbon. A preferred quantity of sludge is from about 0.75 to about 1.25 parts (weight) per part of olenic hydrocarbon. In general, it has been our observation that the lower ratios produce Iless dimerization, fwhile the upper ratios are not economical, since the effect of larger amounts tends to level off.

As with the first aspect of the dimerization process, pressure and residence time are not critical. We have found, however, that more attention is necessary to the temperature in this aspect, since the use of sludge increases the heat of reaction. We have found a temperature in the range of about 15 to about 75 C. to be suitable, with a temperature in the range of about 30 to about 55 C. being preferred. Any residence time in excess of 5 minutes is satisfactory.

While the entire reaction mass from the dimerization step generally is transferred to the alkylation reaction zone, in order to provide a more complete teaching of our invention, it may be well to indicate a typical distillation range for an olefin dimer using this procedure:

ASTM distillation, D-86- F. I.B.P. 168

% 678 Cracked End point In general, any aromatic hydrocarbon which is alkylatable is suitable in the alkylation step. The more suitable aromatic hydrocarbons include benzene, toluene, al'l 0f the xylene isomers, ethylbenzene, and napthalene. Of these, benzene and toluene are preferred. It is to be understood that mixtures of the aromatic hydrocarbons can be used. Also, any of the commercial grades can be employed. Particularly suitable sources of the aromatic hydrocarbons are refinery streams containing substantial amounts of the aromatic hydrocarbons. An example of such a re finery stream is that known as aviation blending component (ABC) which is predominantly toluene and contains minor amounts of benzene and xylene isomers.

We have found that a suitable quantity of aromatic hydrocarbon in this step is in the range of from about 0.2 to about 10.0 parts (weight) per part of olefinic hydroJ carbon employed in the dimerization step. A preferred quantity is in the range of about 1.0 to about 3.0 parts (weight) per part of olefin.

A Friedel-Crafts catalyst is used in the alkylation step. Where an alkylation sludge has been used in the dimerization step it is usually necessary to add make up or enrichment catalyst. Any of the Friedel-Crafts catalysts come within the scope of this aspect of the invention. The term Friedel-Crafts catalyst is believed to be well understood in the art and refers in general to materials such yas the aluminum halides, boron trifluoride, boron trichloride, antimony chlorides, stannic chloride, zinc chloride and mercuric chloride. Of the Friedel-Crafts catalysts aluminum chloride is preferred. The preferred material, aluminum chloride, also includes in situ prepared aluminum chloride, in other words, the reaction product of aluminum metal and hydrogen chloride.

In some cases it is desirable to use a proton-donor promoter ywith the Friedel-Crafts catalyst. Suitable promoters include any material which, when added to the catalyst, yields `a proton. Preferred promoters are hydrogen chloride and water.

A suitable amount of catalyst is from about 0.02 to about 0.25 part (weight) per part of the olefin feedstock used in the dimerization step, with a preferred amount being from about 0.08 to about 0.12 part (weight) per part of olefin.

When aluminum metal and hydrogen chloride are employed as a catalyst, an amount of aluminum is used which is equivalent to that present in the aluminum chloride of the preceding ranges for the catalyst A stoichiometric excess of hydrogen chloride for reaction with the aluminum metal is employed.

When using water as a promoter, we have found an amount of about 0.1 to about 30 percent (-weight) based on the aluminum chloride to be suitable, with an amount distillation. Unreacted benzene is removed overhead, arbitrary intermediate fractions lare removed, and the desired alkyl aromatic hydrocarbons are removed as the bottoms. As indicated previously, we refer to this bottom fraction as dimer alkylate bottoms. Preferably,

the dimer alkylate bottoms is that fraction boiling above t Cut Temperature Range, F. Pressure (mm. Hg)

Benzene IBP l, 149 (ore 392 Bot- 200 n toms Temperature). Intermediate Fraction A IBP 1, 257 20 Intermediate Fraction B 2 2574525- 20 1 IBP=initi il boiling point. 2 Suitable 325, more suitable 375, preferable 400.

In some instances it may be desirable to recycle the fraction designated above as intermediate fraction B to the alkylation reaction zone. Recycle of this fraction increases the amount of the bottoms fraction and decreases the net production of this fraction. =It should be emphasized that recycling is not necessary. It can be done if the economics of the process dictate it.

The dimer alkylate bottoms have a combination of properties Iwhich are believed to be novel and unexpected, and therefore these -materials form one aspect of our invention. Because of the unusual properties of these materials they function as excellent sulfonation stocks. The dimer alklate bottoms of our invention have a particularly high monoalkyl content. This is in contrast to postdodecylbenzene which consists primarily of dialkyl substituted materials. The mono alkyl group of our product is a long (c g., 17 carbon and higher) chain which is branched. The term monoalkyl content as used herein refers to an alkylated aromatic hydrocarbon containing a single long branched-chain group. For example, under our terminology we can refer to mono alkyl toluene, which obviously possesses 1 one-carbon alkyl substituent. The presence of a high mono alkyl content in our product is believed to be the reason it is an excellent sulfonating stock.

In order to characterize the dimer alkylate bottoms of our invention more completely, we list the following properties here:

Percent mono alkyl content 1. Molecular weight (average) Boiling range F. at 20 min. Hg. Sulfonation yield, 1b. RSOaH/lb. alkyla Suitable More Suitable Preferred Property l This is based on mole percent of total aromatic constituents.

of 3 to l0 percent being preferred. However, when using aluminum metal plus hydrogen chloride as the catalyst, we have found that amounts in the range of 4 to 25 percent are preferable.

As with both aspects of the dimerization steps, pressure and residence time are not critical. Also, the temperature is not critical in the alkylation step. We have operated satisfactorily at temperatures in the range of about 5 to about 75 C., with preferred temperatures being in the range of about 25 to about 55 C.

On completion of the alkylation reaction, the reaction product is subjected to a wash 'with a caustic solution. In some cases it will be desira-ble to use an acid and/or water wash in addition to the caustic wash. These steps are well known in the alkylation art and do not form a part of our invention.

The caustic washedV product is then subjected to a In general, the use of the sulfonate prepared from our dimer alklate bottoms, determines the distillation range of the material. For example, in order to prepare high quality overbased detergents for use in lubricants we use a -material boiling above 375 (preferably 400) at 20 mm. Hg. However, the material boiling above 325 F. at 20 mm. Hg is suitable for preparing sulfonates for use as rust inhibitors and emulsifying agents.

In order to describe better our invention, reference is now made to the accompanying drawings. It is to be understood that these drawings are included by way of illustration and not by way of limitation. FIGURE l of the drawings describes our process wherein sulfuric acid is used as a catalyst in the dimerization step. FIGURE 2 describes our process wherein the sludge from the alkylation rector, or a preformed alkylation sludge, is used as the catalyst in the dimerization step.

Referring now to FIGURE 1, cat poly gasoline is introduced Iby means of line 1 to the dimerization reaction vessel 3. Concentrated sulfuric acid is introduced by way of line 2 to the reaction vessel 3, which is equipped with agitation means 4. Upon completion of the dimerization reaction, the spent acid is withdrawn by means of line 5. After withdrawal of the spent acid, the crude dimer is withdrawn by means of lines 5 and 6, being passed to wash vessel 7. A caustic solution is introduced into the Wash vessel by means of line 8. Upon completion of washing of the crude dimer with the caustic solution the spent caustic is withdrawn by means of line 9. The crude dimer then passes by means of lines 9 and 10 to a second wash vessel 12. Caustic solution is introduced by means of line 11 to this second wash vessel 12. Upon completion of the second caustic wash, the spent caustic is withdrawn through line 13. The crude dimer is then passed through lines 13 and 14 to a fractionation tower l15. The fractionation tower `15 separates the desired dimer fraction which is removed by line 17 and the byproducts which are removed overhead by means of line 16. The dimer fraction is then passed through line 17 to the alkylation reactor 21 which is equipped with agiatation means 22. Benzene is fed to the alkylation reactor through line 18. Alumuinum chloride catalyst is fed through line 19, and water as a promoter is fed through line 20. Upon completion of the alkylation reaction, the alkylation sludge is removed by means of line 23. This is followed by removal of the crude alkylate which passes through lines 23 and 24 to a wash vessel 26. A sulfuric acid wash solution is introduced by means of line 25 to this Wash vessel. Upon completion of the washing of the crude alkylate with sulfuric acid, the spent acid sludge is removed by means of line 27. The acid washed crude alkylate is then passed by means of lines 27 and 28 to a second Wash vessel 30. A caustic solution is introduced by means of line 29 into the second wash vessel 30. Upon completion of the caustic wash, the spent caustic is removed by means of line 31. The caustic washed crude alkylate is then passed by means of lines 31 and 32 to a fractionation tower 33. In the fractionation tower 33, benzene is removed overhead by means of line 34. `Intermediate fraction A, which for purposes of illustration includes the material boiling up to 257 F., is withdrawn by means of line 35. Intermediate fraction B, which for purposes of illustration includes the fraction boiling in the range of 257 to 325 F., is withdrawn by means of line 36. The desired dimer alkylate bottoms, which is the fraction boiling above 325 F., is withdrawn by means of line 37 and passed into storage.

Referring now to FIGURE 2, cat poly gasoline is introduced by means of line 1 to the dimerization reaction vessel 3 which is equipped with agitation means 4. Recycle aluminum chloride sludge is passed from the alkylation reactor 9 by means of lines 10 and 2 to the dimerization reactor 3. Upon completion of the dimerization reaction, the reaction mass from the di-merization reactor 3 is passed through line 5 to the alkylation reactor `9. Benzene is introduced into the alkylation reactor through line 6. Aluminum chloride catalyst, for enrichment purposes, is passed through line 7 to the alkylation reactor. Also, water, as a promoter for the alkylation reaction, passes through line 8 to the reactor `9. Upon completion of the alkylation reaction, the aluminum chloride sludge is withdrawn by means of lines and 2 to the dimerization reactor 3. The crude alkylate is withdrawn through lines 10 and `11 to a wash vessel 13, wherein it is subjected to a wash |with a caustic solution which has been introduced into the wash vessel 113 by means of line 12. The spent caustic is removed from the wash vessel 13 by means of line 114. The caustic washed crude alkylate is then passed through lines 14 and to a second Wash vessel 16, where it is subjected to a Water Wash, the vvater being introduced by means of line 17 to the second Wash zone 16. The spent washed solution is removed rfrom the second wash vessel by means of line 18. Following this the crude alkylate passes through lines 18 and 19 to the fractionation tower 20. In the fractionation tower benzene is removed overhead by means of line 21. Intermediate fractions A and B are removed through lines 22 and 23, respectively. The desired dimer alkylate bottoms are removed through line 24 and passed to storage. The intermediate fractions A yand B and the dimer alkylate bottoms have the same distillation ranges as described in connection with FIGURE 1.

In both FIGURES l and 2 a single fractionation tower has been shown for reason of convenience. Generally, in practice, a series of fractionating towers is employed. Regardless of the type of fractionation tower or towers employed, the bottoms fraction always has the distillation range desired herein, or its equivalent.

Both of the above-described processes call for the use of washing steps with caustic soda solution and sulfuric acid. It is to be understood that these steps of washing either the crude dimer or the crude alkylate are old in the art and do not form a part of the subject invention.

In order to disclose more clearly the nature of the present invention and the advantages thereof, reference will hereinafter be -made to certain specific embodiments which illustrate the flexibility of the herein-described process. It should be clearly understood, however, that this is done solely by way of example and is not to be construed as a limitation upon the spirit and scope of the appended claims.

EXAMPLE 1 Dimerization of Cat poly gasoline using sulfuric acid catalyst The dimerization `was carried out in a 12-liter, creased flask, equipped with a stirrer, reflux condenser, thermometer, and a l-liter dropping funnel for catalyst addition. A weight of 6,000 grams of cat poly gasoline was charged to the flask and stirring begun. A weight of 1,200 grams of 95-98 percent assay H2804 Was added through the dropping funnel. (20 weight percent sulfuric acid based on the cat poly gasoline was used.) The dimerization reaction was exothermic, and the rate of acid addition was adjusted to C. and a post-stirring time of one hour was not exceeded. The temperature was also controlled by partially submerging the ask in an ice water bath. After the acid addition was completed, the temperature was adjusted to `35 C. and a poststirring time of one hour from the end of the acid addition was used. The reaction mixture was then transferred into two 6-liter separatory funnels for sludge settling. After overnight settling, 1,484 grams of spent acid was withdrawn and discarded. The product was then washed with two successive l-liter washes of 12.5 percent NaOH solution. The washes were allowed to settle for 1 and 21/2 hours, respectively, then withdrawn and discarded. A weight of 5,498 grams of product was obtained for distillation. The dimerization reaction which occurred is evident from the ASTM distillation D-86, of the starting material (cat poly gasoline) and the product as shown below.

Starting Material Product Dimer (Cat Poly Gasoline) API Gravity 60.0 45.4

ASTM Distillation, D-S F.:

IB P 116 120 5%-. 193 273 10%... 231 372 20%.... 256 451 30% 268 486 40%. 278 508 280 526 30() 542 315 562 346 503 00%. 402 634 634 End polnt 467 634 Recovery, percent. 94 .0 96 .0 Residue, percent 2.0 1 .5 Loss, percent 4.0 2.5

9 EXAMPLE 2 Dimerization of plant dodecene using sulfuric acid catalyst Similar to Example 1, except plant dodecene (from recycle polymerization) was substituted for cat poly gasoline. A weight of 1,575 grams of spent acid catalyst was withdrawn after 3 hours of settling. The caustic washed dimer weighed 5,467 grams. Dimerization of the Iolen is apparent from the following distillation data.

and 0.5 gram of water were added to the flask. This was repeated when two-thirds of the dimer had been charged. The reaction was stirred at C. for 1 hour following the dimer addition, and the reaction mixture was then transferred into a 4-liter separatory funnel for sludge separation. After l hour of settling, 141.8 grams of spent AlCl3 sludge was removed, and the product phase was washed with 65 cc. of 95-98 percent H2804. After 1 hour of settling, the acid sludge was removed; and the product was rewashed with 250 cc. of 25 percent NaOH solution.

Cuts 2, 3, 4, and Ibottoms were reblended for alkylation 10 The caustic wash was removed after 2 hours, and 1,465 reactions as described in later examples. grams of product were recovered for distillation. The fol- Boiun Rm'l Mmmm Weight lowing cuts were obtained from a distillation charge of Cut No. g H g of Cut 1,454.3 gl'amS.

Grams l5 Cut No. Boiling Range, C. at 20 Weight of rrrrrijii::3::::jiijiiiii'irrjarfei; ligi mm. He eur, g. cui; No. 2 F' at amm' 2 557 0 C1117 No. l (Benzene) 8811 Cut No, 3 185-198 C, Y508 .7 Cut N- 2 104 2 Cut No 4" 198o 215o C 2469 Clll N0. 3. 198. 4 Bott5ms 215 aand above 289.0 20 ggtoNnig Loss, holdup and tra 900 Loes, hoi'r'rp eli-d tia 11: 5

EXAMPLE 3 Cut No. 4 and the bottoms samples were reblended for Dimerization of cat poly gasoline using sulfuric acid sulfonation. Sulfonation of this alkylate with 20 percent catalyst 2,- oleum yielded 1.069 Ipounds of RSO3H per pound of alkylate. The sulfonic acid had a combining weight of 446 Similar t0 Example 1 except 'We used 10 Percent H2804 and produced ari oveirbased calcium sulfonate of very catalyst rather than 20 percent used 1n that example. good quality The boiling range of the dimer is shown in the table EXAMPLE 7 below' II QQMVIPLE 4 30 Alkylation of benzene with dodccene polymer using aluminum chloride catalyst Dimerization of cat poly gasoline using sulfuric` acial catalyst Similar to Example I6 except we used only 5 percent A1Cl3 sludge. A weight of 71.3 grams of `bottoms boiling Similar to Example 1 except we used 40 percent H2804 o, ,above 232 Q at 20 mm. Hg was Obtainei catalyst, rather than 20 percent as used in that example. The boiling range of the dimer is shown in the table EXAMPLE 8 below. Dimerizatio'n of cat poly gasoline using aluminum EXAMPLE 5 chloride sludge Diinerzation 0f cut poly gasoline using sulfuric acid 40 This reaction was carried out in a 3-li'ter creased i'lask catalyst equipped with a stiirer, reux condenser, thermometer, Similar to Example 1 except We used 85 percent and a 1liter dropping funnel. A weight xof 566.6 grams of (weight) H2504 as the catalyst. The boiling range of the Cat-p01y gasome Was c harged t0 the flask, 'and all equal dimer is shown in the table below. weight of A1Cl3 alltylation sludge was added during a 30- minute period. During the first 10 minutes of the addi- Dimer as Dimm, as Dimm as tion the temperature of the reaction mass was increased deserrbed described .described from 24 C. to 34 C. by the use of a heating mantle. in Eximpl 111 Eainpl 1n Eample During the remainder of the addition the reaction was held at 35 C. Following the sludge addition the reaction was splt n ijl 44,8 43.4 -4 50 stirred for 1 hour at 35 C. The llask contents were then 1131 175 140 transferred to a separatory funnel, and the two phases g/ey. 380 ggg g were allowed to separate over night.1 A weight of 602.4 wijf" 450 507 292 grams of sludge and 298.9 grams of dimer were obtained. gg, ggg ggg g Afterlcaustic washing, a small portion of the dimer was 50,72: 520 580 ais 55 Submitted for an ASTM distillation. A comparison of $g, ggg ggg the starting .cat poly gasoline and the dimer is shown 807011--.. 582 540 46s by the following distillations. 90% 622 64s 503 95% 540 End point t. 630 648 542 Cat Poly Dimer Recovery, percent 95.0 95.0 97.0 Gasoline API Gravity 58.8 40.7 EXAMPLE 6 As'iilggiistiiiation, D-86, F..- 142 168 Alkylaton of benzene with cat poly gasoline dimer using llgju" 40 iss aluminum chloride catalyst zoaf 22g gli A weight of 1,162 grams of benzene was charged to a lgI 5-liter creased flask equipped with a stirrer, reflux conf denser, thermometer, 500 cc. dropping funnel, and fay 70%: 314 5% cilities for both heating and cooling the flask contents. Stirring was started, and 25 grams (1/2 of total) of AlCl3 959g: 424 6(1) and 1.0 gram (1/2 of total) of water were charged to the 70 End Point 439 flask. The dropping funnel containing 500 grams of dimer i Cracked,

as prepa-red in Example 1 was then attached to the ask, and dimer addition was started immediately. The dimer was added during a 30-minute period. When one-third of the dimer had been charged, another 12.5 grams of A1Cl3 1Usually the entire reaction muss is transferred to the to determine the properties of the olefin dimer.

11 EXAMPLE 9 Dimerization of broad cul dodecene using aluminum chloride alkylation sludge Similar to Example 8 with the exception that the feedstock employed was a cat poly gasoline which had been distilled to remove components boiling `below 350 F. The fraction boiling 'above 350 F. was the feedstock.

tures Similar to Example 8 except dimerizations were carried out at 25 C., 30 C., 45 C., and 55 C. The results are shown below.

Temperature of Dimerization 25 C. 30 C. 45 C. 55 C.

API Gravity 42. 4 42.0 41.0 40. 5 ASTM Dstillation, D-80 F IBI EXAMPLE 11 Alkylation of benzene with cat poly gasoline dimer using aluminum metal and hydrochloric acid as catalyst enrichment This preparation was made with a dimer similar to that described in Example 8. The reaction was carried out in a 5-liter creased flask equipped with stirrer, reflux condenser, thermometer, 1,000 cc. dropping funnel, provisions for both heating and cooling the flask contents and with a fritted glass tube suitable for the addition of HCl gas below the surface of the liquid. The reaction setup was further equipped with a train suitable for scrubbing excess HCl from the vapors. A weight of 1,500 grams of benzene, 509.4 lgrams of spent dimer A1Cl3 sludge as described in Example 8, 5.05 grams Al metal (Reynolds HPS-10 granular) and 2.5 grams of water were charged to the flask `and stirring was started. The dropping funnel containing 477.4 grams of dimer was attached to the flask, and dimer addition was started immediately. The addition of anhydrous hydrogen chloride was also started and maintained throughout the dimer addition at 1,007 cc. per minute. After one-third of the dimer had been added, another 2.6 grams of A1 metal and 2.5 grams of H2O were added to the flask. This was repeated when two-thirds of the dimer had been charged. During the dimer addition, the temperature was held at 40 C. After the dimer addition was completed (30 minutes), the hydrogen chloride rate was increased to 2,014 cc. per minute and the reaction mixture was stirred for 1 hour at 40 C. The reaction mixture was then poured into a 4-liter separatory funnel for sludge Separation. After one hour of settling, 781.9

grams of A1Cl3 sludge was removed; and the product phase was washed with 250 cc. of 25 percent NaOH solution. The spent caustic was removed after 30 minutes, and 1,702 grams of product was recovered for distillation. Results of the distillation are shown below.

Cut No. Weight of Charge Cut No. 1 (Benzene). Cut 2 EXAMPLE 12 Alkylation of toluene with cal poly gasoline dimer eniploying aluminum chloride catalyst and recycle of intermediate fraction This preparation was made with a dimer similar to that prepared in Example 8. The reaction was carried out in a 5liter creased flask equipped with stirrer, reux condenser, thermometer, 1,000 cc. dropping funnel and provisions for both heating and cooling the ask contents. The reactants were as follows:

Grams Toluene 1,500 Spent AlCl3 dimerization sludge 417.3

Intermediate fraction (A portion of the fraction boiling between 124 to 205 C. at 20 mm. Hg

in a preceding reaction similar to the one described herein) 500 Dimer 542.3 A1Cl3 50.0 H2O as promoter 2.0

All of the toluene, dimerization sludge, and intermediate fraction were charged to the flask, initially. The stirrer was started and 25 grams of AlCl3 (1/2 of total) and 1.0 gram of water (1/2 of total) was charged to the flask. The dropping funnel containing the dimer was attached to the flask, and dimer addition was started immediately. The dimer was added over a 30-minute period. When onethird of the dimer had been charged, another 12.5 grams of AlCl3 and 0.5 gram of water were added to the ilask. This was repeated when two-thirds of the dimer had been charged. The reaction was stirred for 30 minutes at 40 C. following the dimer addition. The reaction mixture was then poured into a 4liter separatory funnel for sludge separation. After l hour of settling, 601.5 grams of AlC13 sludge was removed, and the product was washed with 250 cc. of 25 percent NaOH solution. The spent caustic was removed after 1 hour of settling, and 2,379 grams of product was obtained for distillation. The distillation results are shown below.

Cut No. Weight 0I Boiling Range, C. at 20 mm. Hg Cut, g.

The cuts were further characterized by the following analysis.

Sulfonation of a blend of cuts 4 and 5 with 20 percent Alkylation of benzene with dimer of cat poly gasoline Using procedures similar to those described in Examples 1 and 6, alkylate benzenes were produced on a pilot plant scale. Distillation of the crude alkylate gave the following product yields:

Overhead Temperatures, F. At Noted Pressures Percent (Weight) Yields Based On Still Charge Cut No.:

1 IBP, 114; 100 mm. Hg... 61.3 2..-- IBP,256;mm Hg 5.08 1f 3 1.84 0 4 1.90 5.... 1.82 6.. 1.88 7 1. 82 s 1.93 9 1.92 10. 0.57 20 11 1.87 12 IBP 352 13mm H 1.95 13.--. 1.92 14.--. 1.09 15 IBP,367 13.15

. Some of the above cuts were then subjected to further analyses. These analyses lndlcated the following:

Isomer Distribution Molecular Cut Nos. and Blends W ight Percent Percent Percent (Osmometer) Mono Paradi Metadi Other cuts and blends were subjected to ASF M distillations. The results were fas follows:

Blend o Blend of Blend of Cut 2 Cuts 3 Cuts 11 Cuts 11 Through 10 and 12 Through 15 4() API Gravity 34.1 31.6 30.3 30.1 ASTM Distillation,

EXAMPLE 14 This example illustrates the high mono alkyl content of the dimer alkylate bottoms.

The procedure in the dimerization step was similar to Example 8. The charge was as follows:

Gm. Cat poly gasoline 500 Alkylation sludge 500 Gm. Benzene 1500 Aluminum chloride 50 Water 2 Intermediate fraction boiling in the range of 257-425 F. at 20` mm. Hg 183 75 14 After washing, the crude alkylate was subjected to a fractional distillation. The fraction boiling above 425 F. at 20 mm. Hg was collected as the dimer alkylate bottoms. The yield was189 grams of product having a mono alkyl content of 94 percent and a molecular weight of 406.

EXAMPLE 15 This example also illustrates high mono alkyl content of the dimer alkylate bottoms. The procedure in the dimerization step was similar to` Example 8. The charge was as follows:

Gm. Cat poly gasoline 500 Alkylation sludge 500 The yield in this step was 534 gm. of crude dimer and 439 gm. of dimer sludge.

The procedure in the alkylation step was similar to Ex ample 12 except that benzene was used instead of toluene. The crude dimer and dimer sludge were added to the reaction vessel. ln addition, the following materials were added:

Benzene 1500 Aluminum chloride 50 Water 2 Intermediate fraction boiling in the range of 257- 425 F. at 20 mm. Hg 384 After washing, the crude alkylate was subjected to a fractional distillation. The fraction boiling above 425 F. at 20 mm. Hg was collected as the ldimer alkylate bottoms. The yield was 196 gm. of product having a mono alkyl content of percent and a molecular weight of 388.

EXAMPLE 16 This example illustrates oper-ation of our process continuously and passing the entire reaction mass from the dimerization .reactor to the alkylation reactor.

The charge rate to the dimerization reactor was as follows:

Gm./min. Cat poly gasoline 11 Alkylation sludge ll The reactor was maintained at .a temperature not in excess of 104 F. The residence time was 30 minutes.

The efiluent was fed to the alkylation reactor where the temperature was held at 100 F. Additional materials were fed to the :alkylation reactor at the following rates:

Gm./min. Benzene 33 Al metal 0.26 Water 0.05 HC1 (8 theories) 1 8.3

After washing the alkylate, it was subjected to a fractional distillation. The yield of dimer lalkylate bottoms was 36.5 percent base-d on the cat poly gasoline, or 4.02 gm./min. The dimer alkylate bottoms had a mono alkyl content of percent and a molecular weight of 375.

Dimer alkylate bottoms derived from cat poly gasoline and dodecene were used to prepare sulfonic acids. These sulfonic acids were then used to prepare overbased barium sulfonates according to the procedure of U.S. Patent No. 2,861,951. Lubricating oil blends containing these overbased barium sulfonates gave good engine tests. In fact, a majority of the blends tested gave a 480-hour pass in the Caterpillar S-1 test.

In addition, dimer alkylate bottoms derived from cat poly gasoline were used to prepare sulfonic acids, which were then used to prepare an overbased magnesium sulfonate. The procedure employed was that of application 1 The term S theories refers to amount of HC1 required to convert Aleta.

S times the stoichiometric all of the Al metal to A1016.

15 Ser. No. 15,031, led Mar. 31, 1960, and having the same assignee as the present application. The product prepared had yan 'acetic base number of .about 300.

It `is believed to be apparent from the preceding discussion, and particularly from the examples, that the process of our invention can be operated either as a batch process, ia continuous process, or a combination of the two. Generally, in commercial operation a continuous process is preferred.

While particular embodiments of the invention have been described, it will be understood, of course, that the invention is not limited thereto, since many modifications may be made; and it is, therefore, contemplated to cover by the appended claims :any such modifications as fall within the true spirit and scope of the invention.

The invention having thus been described, what is claimed and desired to be secured by Letters Patent is:

1. A process for preparing an olen dimer, said olen idimer on alkylation with an aromatic hydrocarbon producing a product which is particularly suitable for preparing oil-soluble sulfonates, said process comprising: cornmingling in a reaction zone an olefinic material, selected from the group consisting of olefins containing from 3 to about 18 carbon atoms and mixtures thereof, and an alkylation sludge, said sludge being the by-product of the alkylation of an olefin with an alkylatable aromatic hydrocarbon in the presence of a Friedel-Crafts catalyst, to produce said olen dimer.

2. A process for preparing an olefin dimer, said oleiin dimer on alk=ylation with an aromatic hydrocarbon producing a product which is particularly suitable for preparing oilsoluble sulfonates, said process comprising: commingling in a reaction zone an olefinic material, selected from the group consisting of oleiins containing from 3 to about 18 icanbon atoms and Imixtures thereof, and from about 0.25 to about 4.0 parts (by Weight), per part of said olelinic material, of an alkylation sludge, said sludge Ibeing the by-product of the alkaylation of an ole- 1in with an alkylataible aromatic hydrocarbon in the presence of a Friedel-Crafts catalyst, to produce a reaction mass containing said olefin dimer.

3. The process of claim 2 characterized further in that the oleiinic material is a cat poly gasoline having the following distillation range:

F. Initial boiling point 86-500 50 percent range 10U-500 End point range 12S-750 4. The process of claim 3 characterized further in that the cat poly gasoline has the following distillation range:

F. Initial boiling point 135-360 50 percent range 280385 End point range 425-525 5. The process of claim 2 characterized further in that the olefinic material is dodecene fraction.

References Cited UNITED STATES PATENTS 2,637,750 5/1953 Smith et al. 260-671 2,813,917 11/1957 Sharrah 260-6'71 3,070,636 12/1962 Kieras 260-671 XR 3,109,869 11/1963 Chambers etal. 260-671 XR 3,238,249 3/1966 Mirviss et al 260-671 XR OTHER REFERENCES Ferris: Handbook of Hydrocarbons, Academic Press Inc., New York, 1955, pp. 258 and 259 relied upon.

DELBERT E. GANTZ, Primary Examiner.

C. R. DAVIS, Assistant Examiner. 

1. A PROCESS FOR PREPARING AN OLEFIN DIMER, SAID OLEFIN DIMER ON ALKYLATION WITH AN AROMATIC HYDROCARBON PRODUCING A PRODUCT WHICH IS PARTICULARLY SUITABLE FOR PREPARING OIL-SOLUBLE SULFONATES, SAID PROCESS COMPRISING: COMMINGLING IN A REACTION ZONE AN OLEFINIC MATERIAL, SELECTED FROM THE GROUP CONSISTING OF OLEFINS CONTAINING FROM 3 TO ABOUT 18 CARBON ATOMS AND MIXTURES THEREOF, AND AN ALKYLATION SLUDGE, SAID SLUDGE BING THE BY-PRODUCT OF THE ALKYLATION OF AN OLEFIN WITH AN ALKYLATABLE AROMATIC HYDROCARBON IN THE PRESENCE OF A FRIEDEL-CRAFTS CATALYST, TO PRODUCE SAID OLEFIN DIMER. 